The present invention relates to a process for producing para-xylene from toluene-containing feeds incorporating pressure swing adsorption and toluene conversion. The present invention includes a pressure swing adsorption (PSA) process component for separating para-xylene and ethylbenzene from mixed C8 aromatics using a non-acidic, medium pore molecular sieve. The molecular sieve is preferably of the MFI structure type and the process is preferably operated in the vapor phase at elevated temperatures and pressures wherein the temperature is substantially isothermal. The present invention also relates to a method of pressure swing adsorption which includes a plurality of steps and which provides recovery from a mixture comprising C8 aromatics of a substantially pure para-xylene or para-xylene and ethylbenzene product stream and a substantially pure meta-xylene and ortho-xylene product stream.
It is known that certain high surface area, porous substances such as silica gel, activated charcoal, and molecular sieves, including zeolites and other molecular sieves, have certain selective adsorption characteristics useful in separating a hydrocarbon mixture into its component parts.
The selective sorption properties of molecular sieves and zeolites have been disclosed in earlier patents and in literature references. Crystalline molecular sieves and zeolites are shape-selective in that they will admit molecules of specific geometry while excluding other molecules.
The separation of xylene isomers has been of particular interest because of the usefulness of para-xylene in the manufacture of terephthalic acid which is used in the manufacture of polyester fabric. Other components of the C8 aromatic hydrocarbon feedstream from which para-xylene (pX) is generally produced are ortho-xylene (oX), which is used in the manufacture of phthalic anhydride which is used to make phthalate based plasticizers; meta-xylene (mX), which is used in the manufacture of isophthalic acid used in the production of specialty polyester fibers, paints, and resins; and ethylbenzene (EB) which is used in the manufacture of styrene.
A refinery feedstock of aromatic C8 mixtures containing ethylbenzene and xylenes will typically have the following content:
Equilibrium mixtures of C8 aromatic hydrocarbons generally contain about 22 weight percent para-xylene, about 21 weight percent ortho-xylene, and about 48 weight percent meta-xylene in the equilibrium mixture.
Processes to separate xylene isomers include low temperature crystallization, fractional distillation, selective sulfonation with subsequent hydrolysis and selective solvent separation; however, such processes require high operating costs.
The use of faujasite zeolites, which are large pore type X and Y type zeolites, as adsorbents in liquid phase, chromatographic-type separations is well known.
In the petrochemical production chain, one of the most important streams is the C6 to C8 aromatics stream containing benzene, toluene, and xylenes (BTX), which is a source of raw materials for high value downstream products. Of the C8 aromatics, para-xylene (pX) is the most desirable. However, because the boiling points of ethylbenzene (EB), ortho-xylene (oX), meta-xylene (mX) and para-xylene (collectively referred to as xe2x80x9cC8 aromaticsxe2x80x9d) are close, they are difficult to separate by fractional distillation. As a consequence, various alternative methods of separating pX from the C8 aromatics have been developed. Common separation methods are fractional crystallization, which utilizes the difference in freezing points, and liquid phase adsorption (e.g., UOP""s Parex process and IFP""s Eluxyl process), which uses a faujasite zeolite to chromatographically separate pX from the other C8 aromatics. The reject stream from the crystallization process or the raffinate from the adsorption process are depleted in pX, and contain relatively high proportions of EB, oX and mX. These streams are typically sent to a catalyst reactor, where the xylenes are isomerized to equilibrium, and at least a portion of the EB is converted to other products, which can be removed from the C8 aromatics by fractional distillation.
Processes for making pX have typically included combinations of isomerization with fractional crystallization or adsorption separation. FIG. 1 is a schematic representation of known art combination of an isomerization catalyst reactor and a crystallization unit. Crystallization is a separation process that takes advantage of the fact that pX crystallizes before the other isomers, i.e., pX crystallizes at 13.3xc2x0 C. (55.9xc2x0 F.), whereas oX crystallizes at xe2x88x9225.2xc2x0 C. (13.4xc2x0 F.) and mX at xe2x88x9247.9xc2x0 C. (xe2x88x9254.2xc2x0 F.). In the physical system of the three isomers, there are two binary eutectics of importance, the px/mX and the pX/oX. As pX is crystallized from the mixture, the remaining mixture (mother liquor) composition approaches one of these eutectic binaries, depending on the starting composition of the mixture. Therefore, in commercial practice, pX is crystallized so that the binary eutectic is only approached but not reached to avoid co-crystallization of the xylene isomers, which would lower the pX purity. Thus, the key disadvantage for crystallization is restricted pX recovery per pass, due to this eutectic limit of the C8 stream. Typically, the concentration of pX in a mixed C8 aromatic stream at equilibrium is about 22 wt %. In commercial crystallization operations, the eutectic point of this mixture limits the pX removed per pass to about 65% of that amount.
The problem of the eutectic limit for pX crystallization has been recognized for some time. U.S. Pat. No. 5,329,060 discloses that the eutectic point of the crystallization unit can be overcome by use of a selective adsorption zone that enriches the pX feed to the crystallizer by rejecting most of the mX, oX and EB to the isomerization reactor. Specifically, the disclosure teaches using a faujasite-based, liquid phase adsorption process that can either be selective for pX or selective for mX and oX. The result of this process is a stream enriched in pX, but still containing a substantial portion of mX and oX. Similarly, U.S. Pat. No. 5,922,924 discloses combining at least one liquid phase, simulated moving bed adsorption zone with crystallization to produce high purity pX. Again, pX is enriched, but the stream still contains significant mX and oX.
U.S. Pat. No. 3,699,182 discloses use of zeolite ZSM-5 in a process for selective separation of biphenyls from mixtures containing the same and para-disubstituted aromatic isomers from mixtures containing the same, particularly for separating C8 aromatics using ZSM-5 zeolite.
U.S. Pat. No. 3,724,170 discloses chromatographic separation of C8 aromatic mixtures over zeolite ZSM-5 or ZSM-8, which has preferably been reacted with an organic radical-substituted silane, in at least two distinct stages whereby para-xylene and ethylbenzene are selectively absorbed whereas the meta-xylene and ortho-xylene are not adsorbed, removing the unadsorbed meta-xylene and ortho-xylene, eluting the para-xylene followed by the ethylbenzene.
British Pat. No. 1,420,796 discloses use of zeolite ZSM-5 or ZSM-8, preferably ZSM-5 or ZSM-8 zeolites which have been reacted with certain silanes, for adsorptive separation of para-xylene and ethylbenzene from a mixture of para-xylene, ortho-xylene, meta-xylene, and ethylbenzene by adsorption/desorption using two or more columns operated in a parallel manner so that when adsorption is being conducted in one column, desorption can be conducted in a parallel column under such conditions as to obtain a continuously operating process which is said to have faster results than use of a single column alone. It is stated that 250xc2x0 C. (482xc2x0 F.) is a preferred upper limit as operation above 250xc2x0 C. (482xc2x0 F.) may lead to catalytic conversion in the zeolite-containing column.
U.S. Pat. No. 3,729,523 discloses a process for separating and recovering each of the xylene isomers and ethylbenzene wherein a mixture of C8 aromatic hydrocarbons, which may also contain C9 and higher paraffins, is heated to 50xc2x0 F.-500xc2x0 F. (10xc2x0 C.-260xc2x0 C.) and subjected to an adsorption step to recover a first mixture of para-xylene and ethylbenzene and a second mixture comprising meta-xylene, ortho-xylene, and the C9 and higher aromatics. The adsorption is preferably conducted in the presence of a molecular sieve or synthetic crystalline aluminosilicate zeolite as the adsorbent, with ZSM-5, the preferred zeolite. The para-xylene and ethylbenzene are adsorbed and may be recovered by heating the adsorbent, reducing the partial pressure of the sorbed material in the vapor or liquid surrounding the adsorbent, lowering the total pressure of the system or purging with a suitable inert gas or displacement liquid. The resulting para-xylene and ethylbenzene mixture is then subjected to crystallization to recover para-xylene and the mother liquor is subjected to distillation to recover the ethylbenzene.
Chinese Patent Application No. 1136549 discloses selectively adsorbing pX and EB from a C8 isomer stream using silicalite-1 zeolite and then producing  greater than 99.5% purity mX and oX from the portion of the stream not adsorbed. In this process there is a substantial amount of contaminating feedstream in the voids of the silicalite-1 adsorbent which is not removed and comes off the adsorption bed along with the adsorbed pX and EB so that the desorbed stream is not substantially pure pX and EB but contains significant amounts of unseparated oX and mX.
None of these references discloses a process using pressure swing adsorption employing a para-selective adsorbent which is preferably a large crystal, non-acidic, medium pore molecular sieve in connection with a toluene conversion component for producing a C8 aromatic feed.
Molecular sieves are crystalline oxides having pore openings and internal cavities the size of some molecules. Zeolites, a sub-group of molecular sieves, are crystalline aluminosilicates. Another well known sub-group of molecular sieves are aluminophosphates or ALPOs. In general, molecular sieves are classified into three groups based on pore size: small pore molecular sieves with pore diameters from 3-4 xc3x85; medium pore molecular sieves with pores diameters from 4-6 xc3x85; and large pore molecular sieves with pore openings of 6-8 xc3x85. In addition to the molecular size pores, molecular sieves have high adsorption energies and for many years have been used as adsorbents. By selection of the proper pore size, molecular sieves may selectively adsorb molecules of different size. This molecular sieving leads to adsorption and separation of the smaller molecule. Often molecular sieving selectivities are high, 100 or greater. The separation of branched from linear paraffins is a commercial process, which utilizes the small pore A zeolite.
Large pore molecular sieves have also been utilized in the separation of hydrocarbons. In large pore molecular sieves, however, all components diffuse into the pores and the separation is based on differences in adsorption energies. The molecule with the highest bond energy is preferentially adsorbed. Generally, adsorption selectivities are high only when molecules have very different heats of adsorption, for example water and paraffin. For molecules with similar heats of adsorption, the adsorption selectivities are low, ca. 1-4. Xylenes isomers, for example, have similar heats of adsorption in Y zeolite. Due to small differences in heats of adsorption and packing geometry in BaY, pX displays an adsorption selectivity of about 2 compared with the other C8 aromatics. In order to separate pX in sufficient purity for chemical sale, i.e., greater than 99%, many separation stages must be conducted. This type of process operates on principles similar to that of chromatography. Commercial examples of separations of this type are the UOP Parex and IFP Eluxyl liquid phase adsorption processes, which utilize ion exchanged Y zeolites to separate pX from C8 aromatics.
Adsorbents useful in the present invention are based on molecular sieves that selectively adsorb p-xylene within the channels and pores of the molecular sieve while not effectively adsorbing m-xylene and o-xylene C8 isomers (i.e., total exclusion of the larger m-xylene and o-xylene or having much slower adsorption rates compared to p-xylene.).
Molecular sieves are ordered porous crystalline materials, typically formed from silica, alumina, and phosphorus oxide (PO4) tetrahedra, that contain a crystalline structure with cavities interconnected by channels. The cavities and channels within the crystalline structure are uniform in size and may permit selective separation of hydrocarbons based upon molecular dimensions. Generally, the term xe2x80x9cmolecular sievexe2x80x9d includes a wide variety of natural and synthetic crystalline porous materials which typically are based on silica tetrahedra in combination with other tetrahedral oxide materials such as aluminum, boron, titanium, iron, gallium, and the like. In these structures networks of silicon and elements such as aluminum are cross-linked through sharing of oxygen atoms. Substitution of elements such as aluminum or boron for silicon in the molecular sieve structure produces a negative framework charge which must be balanced with positive ions such as alkali metal, alkaline earth metal, ammonium or hydrogen. Molecular sieve structures also may be formed based on phosphates in combination with other tetrahedrally substituted elements such as aluminum.
Adsorbents useful in this invention should not possess catalytic isomerization or conversion activity with respect to the C8 aromatic feedstream. Thus, suitable molecular sieves should be non-acidic. If an element such as aluminum or gallium is substituted in the molecular sieve framework, the sieve should be exchanged with a non-acidic counter-ion, such as sodium, to create a non-acidic sieve adsorbent.
Examples of molecular sieves suitable as adsorbents useful in this invention include zeolitic materials containing pore dimensions in the range of 5 to 6 xc3x85 (10-8 meter), typically 5.1 to 5.7 xc3x85, and preferably 5.3 to 5.6 xc3x85, as measured in cross axes of the pore. This range typically is referred to as xe2x80x9cmedium porexe2x80x9d and typically contains 10-ring tetrahedra structures. Typical examples of medium pore molecular sieves include those with MFI and MEL framework structures as classified in Meier and Olson, xe2x80x9cAtlas of Zeolite Structure Types,xe2x80x9d International Zeolite Association (1987), incorporated herein by reference in its entirety. A small pore molecular sieve, such as A zeolite, which contains 8-ring structures does not have a sufficiently large pore opening to effectively adsorb para-xylene within the sieve. Most large pore molecular sieves, such as mordenite, Beta, LTL, or Y zeolite, that contain 12-ring structures do not adsorb para-xylene selectively with respect to ortho- and meta-xylenes. However, several 12 ring structures, having a smaller effective pore size, for example due to puckering, are potentially useful in the invention, such as structure types MTW (e.g., ZSM-12) and ATO (e.g., ALPO-31).
Specific examples of molecular sieves include ZSM-5 (MFI structure type) and ZSM-11 (MEL structure type) and related isotypic structures. Since suitable adsorbents should not be catalytically reactive to components in the feedstream, the preferable adsorbent useful in this invention is silicalite (MFI structure type), an essentially all silica molecular sieve, which contains minimal amounts of aluminum or other substituted elements. Typically, the silica/alumina ratio of suitable silicalite is above 200 and may range above 1000 depending on the contaminant level of aluminum used in the sieve""s preparation. Other MFI and MEL sieves may be used to the extent they are made non-catalytically active. MFI-based molecular sieves are preferred in this invention with silicalite as the most preferred. Other potentially useful adsorbents include structure types MTT, FER, EUO, MFS, TON, AEL, ATO, NES, and others with similar pore sizes.
A molecular sieve which is not catalytically reactive will typically exhibit less than 10% conversion of pX to mX and oX, and preferably less than 5%, and most preferably less than 1%, at the temperature of operation for the process of the invention.
Attempts have been made to use adsorption with zeolites such as ZSM-5 and ZSM-8 to separate ethylbenzene (EB), para-xylene (pX), meta-xylene (mX), and ortho-xylene (oX) from mixtures of C8 aromatics; however, a major disadvantage of these processes is that the time required to effect desorption of the adsorbed components is too long to provide a commercially useful process. In addition, with acidic zeolites, such as HZSM-5, the high temperatures used to obtain rapid desorption cause catalytic reactions to occur converting pX to mX and oX and converting EB to benzene. Furthermore, with HZSM-5, traces of olefins, which are usually present in commercial feeds, irreversibly chemisorb lowering the adsorption capacity of the zeolite. As a result, frequent reconditioning of the adsorbent (e.g., removal of coke deposits) is required.
Due to the strong adsorption and reactivity of xylenes on acid sites of adsorbents such as HZSM-5, a commercial separation process has not been developed. We describe the use of silicalite in a high temperature process to effect the separation of para-xylene and ethylbenzene from a C8 aromatic mixture without reaction of the adsorbed hydrocarbons. These adsorbent and process modifications solve the previous technical obstacles, which have limited commercial development of a molecular sieving, selective adsorption/desorption process for separation of C8 aromatic hydrocarbons.
The process of the present invention overcomes disadvantages of known processes by using pressure swing adsorption at elevated temperature and pressure with a non-acidic, molecular sieve-containing adsorbent to accomplish a rapid adsorption and desorption of the desired components from a feedstream containing C8 aromatics and provide a rapid separation of the desired components which is suitable for commercial use. A non-acidic molecular sieve, such as silicalite (MFI structure type with little to no aluminum), is used to selectively adsorb pX and EB. Desorption is significantly faster and reactions of the adsorbed molecules (pX and EB) do not occur. In addition, olefins do not adsorb on the silicalite, so the adsorption capacity of the adsorbent remains high and frequent reconditioning is not required.
Many of the chemical and physical properties of xylene isomers and ethylbenzene are very similar making separation difficult. The molecular size of these isomers, however, is slightly different and is determined by the position of methyl substitution. The kinetic diameter of para-xylene and ethylbenzene are approximately 6.0 xc3x85; whereas meta-xylene and ortho-xylene are slightly larger, 6.8 xc3x85. It has been known for many years that, based on these differences in size, medium pore zeolites, such as HZSM-5, can selectively adsorb para-xylene and ethylbenzene [See U.S. Pat. Nos. 3,653,184; 3,656,278; 3,770,841; 3,960,520; 4,453,029; 4,899,017; Wu, et al. STUD. SURF. SCI. CATAL., 28:547(1996); Yan, T. Y., IND. ENG. CHEM. RES. 28:572(1989); and Choudhary, et al., IND. ENG. CHEM. RES. 36:1812(1997)] However, a disadvantage of using HZSM-5 for such separations is that protonation of the aromatic ring by acid sites in ZSM-5 leads to formation of a strong chemical bond [Farneth, et al., LANGMUIR, 4:152(1988)] resulting in low desorption rates and long desorption times at low temperature. As a result, such excessively large amounts of ZSM-5 would be required for commercial scale separation of para-xylene and ethylbenzene under these conditions that such separations are not commercially feasible. Increasing the desorption temperature does increase the desorption rate, which lowers the amount of adsorbent needed; however, the acid sites on the HZSM-5 zeolite also have catalytic properties which cause undesirable isomerization of para-xylene to meta-xylene and ortho-xylene, significantly reducing para-xylene purity. Another disadvantage is that the acid sites strongly adsorb olefins which are typically present along with the C8 aromatics in the feedstream, thus lowering the capacity of the adsorbent to adsorb para-xylene and ethylbenzene. These olefins can only be desorbed at high temperatures. Thus, there is either a loss of adsorption capacity at low temperature or a loss in selectivity at high temperature due to reactions catalyzed by the acid sites.
Disadvantages of the earlier processes are overcome in the present invention by using a pressure swing adsorption process for separating para-xylene and ethylbenzene from mixed C8 aromatics using a non-acidic, medium pore molecular sieve, preferably of the MFI structure type and preferably operating in the vapor phase at elevated temperatures and pressures.
We have found that non-acidic forms of ZSM-5, such as Na-ZSM-5, are preferred adsorbents over HZSM-5. In particular, silicalite is a preferred adsorbent over HZSM-5. Silicalite, an all silica, isostructural form of ZSM-5 has been shown to possess superior properties. Like ZSM-5, silicalite selectively adsorbs pX and EB; however, desorption is significantly faster, since the molecules are only adsorbed physically not chemically, as with HZSM-5. Moreover, pX does not isomerize, even at the elevated temperatures necessary to make the process economically practicable.
In silicalite, a silica analog of H-ZSM-5, pX and EB are selectively adsorbed due to their smaller size. However, unlike H-ZSM-5, silicalite contains no acid sites. As a result, pX and EB are desorbed at high temperature without reaction. At elevated temperature, the desorption rates are high and the cycle times are much shorter. As a result, much less adsorbent is required. Furthermore, the adsorption capacity does not decrease significantly with repeated adsorption/desorption cycles due to adsorption of olefins in the aromatic stream.
The PSA component of the present invention uses selective adsorption (adsorption of the smaller C8 isomers) and selective desorption (i.e., no isomerization upon desorption) at substantially isothermal temperatures to provide a substantially pure product stream of para-xylene and ethylbenzene and a substantially pure stream of ortho-xylene and meta-xylene. The components in these streams can be further separated to provide substantially pure para-xylene, ethylbenzene, ortho-xylene, and meta-xylene products.
The problems of long desorption times or the need for excessively large amounts of adsorbent have made earlier attempts to separate C8 aromatics by molecular sieving commercially impracticable. In addition to these disadvantages, there is also the problem of how to remove C8 aromatic feed that collects in non-selective voids, that is, feed which collects in the non-selective void volume (i.e., large mesopores in the adsorbent, interstitial space between adsorbent particles, and void space in the adsorbent vessel) so that the purity of the desorbed product stream will not be reduced by this material. The art has not recognized how to overcome this problem for C8 aromatics.
The present invention has solved this problem by selectively separating the C8 aromatic feed that is contained in the non-selective void volume so that a high purity stream of para-xylene and ethylbenzene is obtained following desorption. A high purity stream of mX and oX is also obtained by the process of the invention. In one embodiment of the invention this high purity stream of mX/oX is obtained by separating the mX/oX from the non-selective void volume prior to desorbing the pX/EB.
The use of the process of the present invention in para-xylene production facilities would significantly reduce the amount of meta-xylene and ortho-xylene sent to a crystallization section or a simulated moving bed liquid chromatography section, thus opening up capacity and decreasing operating costs. This would increase the para-xylene concentration and yields. Having a stream with a greater concentration of para-xylene going to the crystallization section may also make it possible to eliminate a crystallizer, for example, a low-temperature ethylene unit might not be needed if a feed with a higher concentration of para-xylene is being crystallized to recover para-xylene. This would also save equipment costs and reduce the amount of energy necessary to conduct the crystallization and purification of para-xylene.
The present invention is a process for producing para-xylene from toluene-containing feeds which incorporates toluene conversion with pressure swing adsorption. This invention comprises a process for the production of para-xylene using a pressure-swing adsorption (PSA) process disclosed herein, in combination with toluene-based processes for the production of para-xylene. The main advantage is that both crystallization and simulated moving bed adsorption chromatography (SiMBAC) are most efficiently operated when used to purify a concentrated stream of PX. The PSA technology can perform such a bulk separation to further concentrate a PX-containing stream before, optionally, sending a more concentrated PX stream to crystallization or SiMBAC. With such a process, portions of the various separation processes can be redesigned to decrease both capital and operating costs. In addition, the overall yield of PX will be improved by using the PSA technology.
The present invention relates to a pressure swing adsorption (PSA) process for separating para-xylene, or para-xylene and ethylbenzene, from a mixture containing C8 aromatics produced by conversion of a toluene-containing feedstream. The present invention is a process for producing para-xylene from a toluene feed which integrates pressure swing adsorption and toluene conversion. The present invention includes a pressure swing adsorption (PSA) process component for separating para-xylene and ethylbenzene from mixed C8 aromatics using a para-selective adsorbent, preferably a para-selective, non-acidic molecular sieve, more preferably a para-selective, non-acidic, medium pore molecular sieve, and a toluene conversion component for producing a C8 aromatic feed that is separated by means of pressure swing adsorption. Generally the C8 aromatic feedstream from the toluene conversion component will be separated from unreacted toluene by distillation, crystallization, or simulated moving bed chromatography prior to being subjected to PSA.
The PSA component of the present invention relates to a method for separating para-xylene from a gaseous feed mixture containing meta-xylene and ortho-xylene under substantially isothermal conditions comprising:
(a) adsorbing the mixture onto an adsorbent containing a para-selective adsorbent capable of selectively adsorbing para-xylene at a temperature and pressure at which at least 0.01 grams of para-xylene may be adsorbed per gram of para-selective adsorbent;
(b) producing a first effluent stream containing a mixture of ortho-xylene and meta-xylene, having no more than a total of about 20 mole percent of para-xylene based on total C8 aromatics, preferably less than about 20 mole percent of para-xylene, more preferably no more than about 15 mole percent of para-xylene, more preferably less than about 15 mole percent of para-xylene, more preferably no more than about 10 mole percent of para-xylene, more preferably less than about 10 mole percent of para-xylene, more preferably no more than about 5 mole percent of para-xylene, more preferably less than about 5 mole percent of para-xylene, more preferably no more than about 3 mole percent of para-xylene, more preferably less than about 3 mole percent of para-xylene, more preferably no more than about 1 mole percent of para-xylene, and most preferably less than about 1 mole percent of para-xylene based on total C8 aromatics;
(c) selectively removing feed from the non-selective void volume;
(d) selectively desorbing para-xylene by decreasing partial pressure of para-xylene; and
(e) collecting a stream containing para-xylene and having no more than a total of about 50 mole percent of meta-xylene and ortho-xylene based on total C8 aromatics; preferably less than about 50 mole percent of meta-xylene and ortho-xylene, more preferably no more than about 45 mole percent of meta-xylene and ortho-xylene, more preferably less than about 45 mole percent of meta-xylene and ortho-xylene, more preferably no more than about 40 mole percent of meta-xylene and ortho-xylene, preferably less than about 40 mole percent of meta-xylene and ortho-xylene, more preferably no more than about 35 mole percent of meta-xylene and ortho-xylene, more preferably less than about 35 mole percent of meta-xylene and ortho-xylene, more preferably no more than about 30 mole percent of meta-xylene and ortho-xylene, more preferably less than about 30 mole percent of meta-xylene and ortho-xylene, more preferably no more than about 25 mole percent of meta-xylene and ortho-xylene, more preferably less than about 25 mole percent of meta-xylene and ortho-xylene, more preferably no more than about 20 mole percent of meta-xylene and ortho-xylene, more preferably less than about 20 mole percent of meta-xylene and ortho-xylene, more preferably no more than about 15 mole percent of meta-xylene and ortho-xylene, more preferably less than about 15 mole percent of meta-xylene and ortho-xylene, more preferably no more than about 10 mole percent of para-xylene, more preferably less than about 10 mole percent of meta-xylene and ortho-xylene, more preferably no more than about 5 mole percent of meta-xylene and ortho-xylene, and most preferably less than about 5 mole percent of meta-xylene and ortho-xylene based on total C8 aromatics.
A practice of the invention involves principally proceeding by repeated cycles comprising in an individual cycle the above steps (a) through (e).
Additional embodiments of the PSA component of the process of the present invention are described below.
In step (a) of the process of the present invention described above, it is preferable that at least 0.01 g of para-xylene be adsorbed per gram of para-selective adsorbent contained in the adsorbent; more preferable that at least 0.02 g of para-xylene be adsorbed per gram of para-selective adsorbent contained in the adsorbent; and even more preferable that at least 0.03 g of para-xylene be adsorbed per gram of para-selective adsorbent contained in the adsorbent.
Preferably, the first effluent stream mixture of ortho-xylene and meta-xylene produced in the process of the invention, as, for example, in step (b) above, will contain no more than about 20 mole percent of para-xylene based on total C8 aromatics, preferably less than about 20 mole percent of para-xylene, more preferably no more than about 15 mole percent of para-xylene, more preferably less than about 15 mole percent of para-xylene, more preferably no more than about 10 mole percent of para-xylene, more preferably less than about 10 mole percent of para-xylene, more preferably no more than about 5 mole percent of para-xylene, more preferably less than about 5 mole percent of para-xylene, more preferably no more than about 3 mole percent of para-xylene, more preferably less than about 3 mole percent of para-xylene, and still more preferably no more than about 1 mole percent of para-xylene, and even more preferably less than about 1 mole percent of para-xylene.
Preferably, the para-xylene-containing stream collected in the process of the invention, as, for example, in step (e) above, will contain no more than a total of about 50 mole percent of meta-xylene and ortho-xylene based on total C8 aromatics, preferably less than a total of about 50 mole percent of meta-xylene and ortho-xylene, more preferably no more than a total of about 45 mole percent of meta-xylene and ortho-xylene, preferably less than a total of about 45 mole percent of meta-xylene and ortho-xylene, more preferably no more than a total of about 40 mole percent of meta-xylene and ortho-xylene, preferably less than a total of about 40 mole percent of meta-xylene and ortho-xylene, more preferably no more than a total of about 30 mole percent of meta-xylene and ortho-xylene, preferably less than a total of about 30 mole percent of meta-xylene and ortho-xylene, preferably no more than a total of about 25 mole percent of meta-xylene and ortho-xylene; preferably less than a total of about 25 mole percent of meta-xylene and ortho-xylene; more preferably no more than a total of about 20 mole percent of meta-xylene and ortho-xylene, preferably less than a total of about 20 mole percent of meta-xylene and ortho-xylene, more preferably no more than a total of about 15 mole percent of meta-xylene and ortho-xylene, preferably less than a total of about 15 mole percent of meta-xylene and ortho-xylene, more preferably no more than a total of about 10 mole percent of meta-xylene and ortho-xylene, preferably less than a total of about 10 mole percent of meta-xylene and ortho-xylene, more preferably no more than a total of about 5 mole percent of meta-xylene and ortho-xylene, and most preferably less than a total of about 5 mole percent of meta-xylene and ortho-xylene based on total C8 aromatics.
In the most preferred embodiments of the invention, the effluent product stream containing para-xylene, or para-xylene and ethylbenzene, will be substantially free of meta-xylene and ortho-xylene, and the effluent product stream containing meta-xylene and ortho-xylene will be substantially free of para-xylene, or substantially free of para-xylene and ethylbenzene.
The adsorbent is preferably a para-selective adsorbent, more preferably a para-selective, non-acidic molecular sieve, more preferably a para-selective, non-acidic, medium pore molecular sieve. Preferably, the molecular sieve comprises silicalite, and more preferably, the molecular sieve comprises orthorhombic crystals of silicalite having an average minimum dimension of at least about 0.2 xcexcm.
In one embodiment of the invention, the adsorbent comprises a para-selective adsorbent and a binder, preferably a para-selective, non-acidic medium pore molecular sieve and a binder. The binder is preferably selected from the group consisting of clay, alumina, silica, titania, zirconia, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia, silica-magnesia-zirconia, and aluminum phosphate.
A para-selective adsorbent is a molecular sieve that, when subjected to an equal molar mixture of C8 aromatics at 50xc2x0 C., adsorbs pX and EB preferentially over mX and oX, such that the total pX and EB in the adsorbate is at least about 75% relative to the total C8 aromatics.
A preferred para-selective adsorbent, when subjected to an equal molar mixture of C8 aromatics at 50xc2x0 C., will adsorb pX and EB preferentially over mX and oX, such that the total pX and EB in the adsorbate is greater than about 75% relative to the total C8 aromatics.
A more preferred para-selective adsorbent, when subjected to an equal molar mixture of C8 aromatics at 50xc2x0 C., will adsorb pX and EB preferentially over mX and oX, such that the total pX and EB in the adsorbate is at least about 80% relative to the total C8 aromatics, even more preferably, at least about 85% relative to the total C8 aromatics, still more preferably, at least about 90% relative to the total C8 aromatics; and yet more preferably, at least about 95% relative to the total C8 aromatics; and most preferably, at least about 97% relative to the total C8 aromatics.
In the present invention the operating temperature is preferably from about 350xc2x0 F. to about 750xc2x0 F. and the operating pressure is preferably from about 30 psia to about 400 psia (from about 206 kPa to about 2760 kPa).
The PSA component of the present invention additionally relates to a method to separate para-xylene and ethylbenzene from a gaseous feed mixture containing meta-xylene and ortho-xylene under substantially isothermal conditions comprising:
(a) adsorbing the mixture onto an adsorbent containing a para-selective adsorbent capable of selectively sorbing para-xylene and ethylbenzene at a temperature and pressure at which at least 0.01 grams of para-xylene and ethylbenzene may be adsorbed per gram of adsorbent;
(b) producing a first effluent stream containing a mixture of ortho-xylene and meta-xylene having no more than a total of about 25 mole percent of para-xylene and ethylbenzene based on total C8 aromatics, preferably less than about 25 mole percent of para-xylene and ethylbenzene, more preferably no more than about 20 mole percent of para-xylene and ethylbenzene, more preferably less than about 20 mole percent of para-xylene and ethylbenzene, more preferably no more than about 15 mole percent of para-xylene and ethylbenzene, more preferably less than about 15 mole percent of para-xylene and ethylbenzene, more preferably no more than about 10 mole percent of para-xylene and ethylbenzene, more preferably less than about 10 mole percent of para-xylene and ethylbenzene, more preferably no more than about 5 mole percent of para-xylene and ethylbenzene, more preferably less than about 5 mole percent of para-xylene and ethylbenzene, more preferably no more than about 3 mole percent of para-xylene and ethylbenzene, more preferably less than about 3 mole percent of para-xylene and ethylbenzene, more preferably no more than about 1 mole percent of para-xylene and ethylbenzene, and most preferably less than about 1 mole percent of para-xylene and ethylbenzene based on total C8 aromatics;
(c) selectively removing feed from the non-selective void volume;
(d) selectively desorbing para-xylene and ethylbenzene by decreasing partial pressure of para-xylene and ethylbenzene; and
(e) collecting a stream containing para-xylene and ethylbenzene and having no more than a total of about 50 mole percent of meta-xylene and ortho-xylene based on total C8 aromatics.
A practice of the invention involves principally proceeding by repeated cycles comprising in an individual cycle the above steps (a) through (e).
In a preferred embodiment of the above process, the effluent comprising meta-xylene and ortho-xylene collected in step (b) will be substantially free of ethylbenzene and para-xylene.
In a preferred embodiment of the above process, the second effluent product comprising ethylbenzene and para-xylene collected in step (e) will be substantially free of meta-xylene and ortho-xylene.
In step (a) of the process of the present invention described above, it is preferable that at least 0.01 g of para-xylene and ethylbenzene be adsorbed per gram of adsorbent; more preferable that at least 0.02 g of para-xylene and ethylbenzene be adsorbed per gram of adsorbent; still more preferable that at least 0.03 g of para-xylene and ethylbenzene be adsorbed per gram of adsorbent.
The present invention also relates to a process for separating a mixture of organic compounds having normal boiling points in a temperature range from about 800xc2x0 C. to about 1600xc2x0 C., which process comprises:
(a) providing an adsorbent bed comprising a para-selective adsorbent which exhibits capacity to selectively adsorb and desorb para-xylene and ethylbenzene under substantially isothermal conditions of temperature at operating pressure, disposed in a vessel having at least one inlet and at least one outlet such that gas entering an inlet passes through the adsorbent bed to an outlet, and containing a purge gas substantially free of C8 aromatic compounds;
(b) flowing a gaseous feed mixture comprising xylenes and ethylbenzene into the bed through one or more of the vessel inlets, and collecting an effluent from one or more of the outlets comprising purge gas substantially free of C8 aromatic compounds while selectively adsorbing para-xylene and ethylbenzene from the gaseous mixture under substantially isothermal conditions in the bed;
(c) continuing the flow of gaseous feed and collecting from one or more of the outlets and segregating a second effluent comprising m-xylene and o-xylene having no more than about 25 mole percent of p-xylene and ethylbenzene;
(d) stopping the feed mixture flowing into the bed through one or more inlets just prior to breakthrough (i.e., the adsorption front is close to the exit end of the adsorbent column), and flowing purge gas preferably in a direction counter to the direction of the C8 aromatic feed, while maintaining substantially isothermal conditions in the bed, and collecting from one or more of the outlets an effluent gaseous mixture of C8 aromatic feed until effluent at the outlet contains no more than about 50 mole percent of meta-xylene and ortho-xylene;
(e) continuing the flow of purge gas and collecting from one or more of the outlets and segregating an effluent comprising ethylbenzene and p-xylene which contains no more than about 50 mole percent of meta-xylene and ortho-xylene; and
(f) repeating steps (b) through (e).
In a preferred embodiment of the above process, the effluent comprising m-xylene and o-xylene collected in step (c) will be substantially free of para-xylene and ethylbenzene.
In a preferred embodiment of the above process, in step (d) the effluent gaseous mixture of C8 aromatic feed will be collected until the effluent at the outlet is substantially free of meta-xylene and ortho-xylene.
In a preferred embodiment of the above process, the effluent comprising ethylbenzene and p-xylene collected in step (e) will be substantially free of meta-xylene and ortho-xylene
A practice of the invention involves principally proceeding by repeated cycles comprising in an individual cycle the above steps (a) through (f).
In a preferred embodiment of the process, the flow of the purge gas is counter current to the flow of the gaseous feed mixture.
In one embodiment of the process, steps (b) through (e) are repeated with a cycle time of from about 2 minutes to about 200 minutes, preferably with a cycle time of from about 3 minutes to about 50 minutes, more preferably with a cycle time of from about 3 minutes to about 30 minutes.
In an embodiment of the process at least a portion of the effluent gaseous mixture collected in step (d) is admixed with the gaseous feed mixture in subsequent cycles.
In another embodiment of the process, the purge gas comprises hydrogen, and steps (b) through (e) are repeated with a cycle time of from about 3 minutes to about 30 minutes under substantially isothermal conditions at a temperature of about 350xc2x0 F. to about 750xc2x0 F. and at constant operating pressure at a pressure of at least about 30 psia.
An additional embodiment of the invention comprises a process for separating a mixture of ethylbenzene and the isomers of xylene, which process comprises:
(a) providing an adsorbent bed comprising a para-selective adsorbent which exhibits capacity to selectively adsorb and desorb para-xylene and ethylbenzene under substantially isothermal conditions at operating pressure, disposed in a vessel having at least one inlet and at least one outlet such that gas entering an inlet passes through the particulate bed to an outlet and pressurizing the vessel with a mixture comprising meta-xylene and ortho-xylene to a preselected pressure for adsorption;
(b) flowing a gaseous feed mixture comprising xylene isomers and ethylbenzene into the adsorbent bed through one or more inlets and displacing the meta-xylene and ortho-xylene in the vessel while selectively adsorbing ethylbenzene and para-xylene from the gaseous feed mixture under substantially isothermal conditions in the adsorbent bed;
(c) collecting from one or more of the outlets a first effluent product comprising meta-xylene and ortho-xylene which contains no more than a total of about 25 mole percent of ethylbenzene and para-xylene while maintaining substantially isothermal conditions in the adsorbent bed and the flow of feed at the pressure for adsorption;
(d) replacing the feed mixture flowing into the bed though one or more inlets with a purge gas comprising para-xylene and ethylbenzene substantially free of meta-xylene and ortho-xylene while maintaining the pressure for adsorption and substantially isothermal conditions in the bed, and collecting from one or more of the outlets a gaseous mixture comprising feed;
(e) reducing the pressure to desorb ethylbenzene and para-xylene while maintaining substantially isothermal conditions in the bed; and
(f) collecting a second effluent product comprising ethylbenzene and para-xylene which contains no more than a total of about 50 mole percent of meta-xylene and ortho-xylene.
In a preferred embodiment of the above process:
(a) the flow of said para-xylene and ethylbenzene purge gas is countercurrent to the flow of the gaseous feed mixture;
(b) the para-xylene and ethylbenzene effluent flow during depressurization is countercurrent to the flow of the gaseous feed mixture; and
(c) the flow of meta-xylene and ortho-xylene to pressurize the vessel is countercurrent to the feed gas flow.
In a preferred embodiment of the above process, the effluent comprising meta-xylene and ortho-xylene collected in step (c) will be substantially free of ethylbenzene and para-xylene.
In a preferred embodiment of the above process, the second effluent product comprising ethylbenzene and para-xylene collected in step (f) will be substantially free of meta-xylene and ortho-xylene.
A further embodiment of the invention comprises a process for separating a mixture of ethylbenzene and the isomers of xylene, which process comprises:
(a) providing at least two adsorbent beds containing a para-selective adsorbent which exhibits capacity to selectively adsorb and desorb para-xylene and ethylbenzene under substantially isothermal conditions at operating pressure, disposed in sequentially connected or interconnected vessels, each having at least one inlet and at least one outlet such that gas entering an inlet passes through the particulate bed to an outlet, and pressurizing a first vessel with a mixture comprising meta-xylene and ortho-xylene to a preselected pressure for adsorption;
(b) flowing a gaseous feed mixture comprising xylene isomers and ethylbenzene into the adsorbent bed in the first vessel though one or more inlets and displacing the meta-xylene and ortho-xylene in the vessel while selectively adsorbing ethylbenzene and para-xylene from the gaseous feed mixture under substantially isothermal conditions in the adsorbent bed;
(c) collecting from one or more of the outlets a first effluent product comprising meta-xylene and ortho-xylene which contains no more than a total of about 25 mole percent of ethylbenzene and para-xylene while maintaining substantially isothermal conditions in the adsorbent bed and the flow of feed at the pressure for adsorption;
(d) stopping the flow of feed and reducing the pressure in the first vessel sufficiently to permit removal of at least a portion of the feed from non-selective voids while maintaining substantially isothermal conditions in the bed by equalizing the pressure in the first vessel with the pressure in the second vessel which is at a lower pressure;
(e) further reducing the pressure in the first vessel to desorb ethylbenzene and para-xylene while maintaining substantially isothermal conditions in the bed; and
(f) collecting a second effluent product comprising ethylbenzene and para-xylene which contains no more than a total of about 50 mole percent of meta-xylene and ortho-xylene.
In a preferred embodiment of the above process, the effluent comprising meta-xylene and ortho-xylene collected in step (c) will be substantially free of ethylbenzene and para-xylene.
In a preferred embodiment of the above process, the second effluent product comprising ethylbenzene and para-xylene collected in step (f) will be substantially free of meta-xylene and ortho-xylene.
In the above process, following step (f), a purge gas comprising meta-xylene and ortho-xylene can be added to the first vessel to displace para-xylene and ethylbenzene in the non-selective voids, and an effluent comprising the para-xylene and ethylbenzene is collected.
Another embodiment of the present invention comprises a process for separating a mixture of ethylbenzene and the isomers of xylene, which process comprises:
(a) providing an adsorbent bed comprising a para-selective adsorbent which exhibits capacity to selectively adsorb and desorb para-xylene and ethylbenzene under substantially isothermal conditions at operating pressure, disposed in a vessel having at least one inlet and at least one outlet such that gas entering an inlet passes through the particulate bed to an outlet and pressurizing the vessel with a mixture of substantially meta-xylene and ortho-xylene to a preselected pressure for adsorption;
(b) flowing a gaseous feed mixture comprising xylene isomers and ethylbenzene into the adsorbent bed though one or more inlets and displacing the meta-xylene and ortho-xylene in the vessel while selectively adsorbing ethylbenzene and para-xylene from the gaseous feed mixture under substantially isothermal conditions in the adsorbent bed;
(c) collecting from one or more of the outlets a first effluent product comprising meta-xylene and ortho-xylene xylene which contains no more than a total of about 25 mole percent of ethylbenzene and para-xylene while maintaining substantially isothermal conditions in the adsorbent bed and the flow of feed at the pressure for adsorption;
(d) stopping the flow of feed and reducing operating pressure to a pressure at which para-xylene and ethylbenzene desorb while maintaining substantially isothermal conditions in the bed; and
(e) collecting a second effluent product comprising ethylbenzene and para-xylene which contains no more than a total of about 50 mole percent of meta-xylene and ortho-xylene.
In the above embodiment, preferably, following step (e), a purge gas comprising meta-xylene and ortho-xylene is added to the first vessel to displace para-xylene and ethylbenzene in the non-selective voids, and an effluent comprising the para-xylene and ethylbenzene is collected.
In a preferred embodiment of the above process, the effluent comprising meta-xylene and ortho-xylene collected in step (c) will be substantially free of ethylbenzene and para-xylene.
In a preferred embodiment of the above process, the second effluent product comprising ethylbenzene and para-xylene collected in step (e) will be substantially free of meta-xylene and ortho-xylene.
In the embodiments of the pressure swing adsorption process of the present invention described above, it is preferred that the first effluent stream mixture of ortho-xylene and meta-xylene produced in the process of the invention will contain no more than about 20 mole percent of para-xylene, more preferably less than about 20 mole percent of para-xylene, more preferably no more than about 15 mole percent of para-xylene, more preferably less than about 15 mole percent of para-xylene, more preferably no more than about 10 mole percent of para-xylene, more preferably less than about 10 mole percent of para-xylene, more preferably no more than about 5 mole percent of para-xylene, more preferably less than about 5 mole percent of para-xylene, more preferably no more than about 3 mole percent of para-xylene, more preferably less than about 3 mole percent of para-xylene, and still more preferably no more than about 1 mole percent of para-xylene.
In the embodiments of the pressure swing adsorption process of the present invention described above wherein the first effluent mX/oX stream contains both para-xylene and ethylbenzene, it is preferred that the first effluent stream mixture of ortho-xylene and meta-xylene produced in the process of the invention will contain no more than about 25 mole percent of para-xylene and ethylbenzene based on total C8 aromatics, preferably less than about 25 mole percent of para-xylene and ethylbenzene, more preferably no more than about 20 mole percent of para-xylene and ethylbenzene, more preferably less than about 20 mole percent of para-xylene and ethylbenzene, more preferably no more than about 15 mole percent of para-xylene and ethylbenzene, more preferably less than about 15 mole percent of para-xylene and ethylbenzene, more preferably no more than about 10 mole percent of para-xylene and ethylbenzene, more preferably less than about 10 mole percent of para-xylene and ethylbenzene, more preferably no more than about 5 mole percent of para-xylene and ethylbenzene, more preferably less than about 5 mole percent of para-xylene and ethylbenzene, more preferably no more than about 3 mole percent of para-xylene and ethylbenzene, more preferably less than about 3 mole percent of para-xylene and ethylbenzene, and still more preferably no more than about 1 mole percent of para-xylene and ethylbenzene.
In the embodiments of the pressure swing adsorption process of the present invention described above, it is preferred that the para-xylene-containing stream collected in the process of the invention will contain no more than a total of about 50 mole percent of meta-xylene and ortho-xylene based on total C8 aromatics, preferably less than a total of about 50 mole percent of meta-xylene and ortho-xylene, more preferably no more than a total of about 45 mole percent of meta-xylene and ortho-xylene, preferably less than a total of about 45 mole percent of meta-xylene and ortho-xylene, more preferably no more than a total of about 40 mole percent of meta-xylene and ortho-xylene, preferably less than a total of about 40 mole percent of meta-xylene and ortho-xylene, more preferably no more than a total of about 30 mole percent of meta-xylene and ortho-xylene, preferably less than a total of about 30 mole percent of meta-xylene and ortho-xylene, preferably no more than a total of about 25 mole percent of meta-xylene and ortho-xylene; preferably less than a total of about 25 mole percent of meta-xylene and ortho-xylene; more preferably no more than a total of about 20 mole percent of meta-xylene and ortho-xylene, preferably less than a total of about 20 mole percent of meta-xylene and ortho-xylene, more preferably no more than a total of about 15 mole percent of meta-xylene and ortho-xylene, preferably less than a total of about 15 mole percent of meta-xylene and ortho-xylene, more preferably no more than a total of about 10 mole percent of meta-xylene and ortho-xylene, preferably less than a total of about 10 mole percent of meta-xylene and ortho-xylene, more preferably no more than a total of about 5 mole percent of meta-xylene and ortho-xylene, and most preferably less than a total of about 5 mole percent of meta-xylene and ortho-xylene based on total C8 aromatics.
In the most preferred embodiments of the pressure swing adsorption process of the present invention, the effluent product stream containing para-xylene, or para-xylene and ethylbenzene, will be substantially free of meta-xylene and ortho-xylene, and the effluent product stream containing meta-xylene and ortho-xylene will be substantially free of para-xylene, or substantially free of para-xylene and ethylbenzene.
A purge gas substantially free of C8 aromatic compounds will contain no more than about 10 wt %, and preferably less than about 5 wt %, and most preferably less than about 2 wt % of C8 aromatic compounds.
A fraction or stream substantially free of p-xylene and ethylbenzene will contain no more than a total of about 5 mole percent of p-xylene and ethylbenzene based on total C8 aromatics.
A fraction or stream substantially free of para-xylene will contain no more than about 5 mole percent of para-xylene based on total C8 aromatics. Preferably such a fraction will contain no more than about 1 mole percent of para-xylene based on total C8 aromatics.
For those process steps conducted at constant pressure, those skilled in the art will recognize that during operation there may be slight variations in pressure due to pressure drops across the system or changes in flows; however the pressure will remain substantially constant.
A fraction or stream substantially free of m-xylene and o-xylene will contain no more than a total of about 25 mole percent of m-xylene and o-xylene based on total C8 aromatics. Preferably such a stream will contain no more than about 20 mole percent, more preferably no more than about 15 mole percent; still more preferably no more than about 10 mole percent; and most preferably no more than about 5 mole percent of m-xylene and o-xylene based on total C8 aromatics.
The PSA component of the present invention also relates to a method of pressure swing adsorption which includes a plurality of steps and which provides recovery from a mixture comprising C8 aromatics of a product stream of p-xylene or p-xylene and ethylbenzene which is substantially free of m-xylene and o-xylene as well as a product stream of meta-xylene and ortho-xylene which is substantially free of p-xylene and ethylbenzene. The PSA component of the present invention provides a pressure swing adsorption process whereby there can be obtained from a feed comprising C8 aromatics a high yield of a high purity product stream of p-xylene and ethylbenzene and also a high yield of a high purity product stream of m-xylene and o-xylene.